Plastic compositions

ABSTRACT

Plastic compositions containing a three component system consisting of (1) polyethylene, (2) certain bis-phenoxy compounds having the formula: ##STR1## WHEREIN Z is bromine, m and m&#39;  are each integers having a value of 5, and alkylene is a straight chain carbon group having 1 to 3 carbon atoms, and (3) an enhancing agent, hereinafter defined.

RELATED PATENT APPLICATIONS

This application is a continuation-in-part of a copending application Ser. No. 330,782, filed Feb. 8, 1973 now U.S. Pat. No. 4,038,248. The entire specification of Ser. No. 330,782, is to be considered as incorporated herein by reference.

PRIOR ART

The prior art considered in conjunction with the preparation of this application is as follows: U.S. Pat. Nos. 1,979,145; 2,130,990; 2,186,367; 2,263,444; 2,329,033; 2,488,499; 2,738,351, 2,797,246; 2,930,815; 3,385,819; 3,549,591; 3,560,441; 3,646,591; 3,658,634; 3,666,692; 3,697,456; 3,686,320; 3,717,609; 3,763,243; 3,787,506; German Pat. No. 891,549; German Pat. No. 1,139,636; German Pat. No. 2,054,522; Japanese Pat. No. (72) 14,500 (and as cited in Volume 77, Chemical Abstracts, column 153737k, 1972); Chemical Abstracts, Volume 13, column 4485; Chemical Abstracts, Volume 31, column 70459; Chemical Abstracts, Volume 52 (1958), column 4543-4544; Journal of the Chemical Society, pages 2972-2976 (1963); Journal of the American Chemical Society, Volume 57 (1935), pages 572-574 and Volume 76 (1954) page 2993; Journal of the Science of Food and Agriculture, Volume 20 (1969), pages 748-754; and Philippine Journal of Science, Volume 34 (1927), page 159. All of these publications are to be considered as incorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to plastic compositions containing a polyethylene polymer. More specifically, the present invention covers plastic compositions containing a three component system which consists of polyethylene, certain bis-phenoxy compounds (herinafter defined) as a flame retardant for said plastic compositions, and an enhancing agent (hereinafter defined) for said flame retardants.

Polyethylene and utility thereof are known in the art as exemplified by Polyolefin Plastics, T. O. J. Kresser, (Van Nostrand Reinhold Plastics Applications Series), Van Nostrand Reinhold Company, New York, 1969 and Modern Plastics Encyclopedia 1972-1973, Vol. 49: No. 10A, October, 1972, pages 78, 83, 85, 86, 89-92, 97 and 158-160 and which publications are in toto incorporated herein by reference.

The need for flame retarding polyethylene has also been recognized in the art as exemplified by U.S. Pat. Nos. 3,133,038, 3,347,822 and 3,422,048 and Modern Plastics Encyclopedia, ibid, pages 456 through 458 and which publications are in toto incorporated herein by reference.

The prior art has specifically recognized the problems of finding suitable flame retradants for polyethylene in view of the fact that polymer systems differ substantially in both flammability characteristics and physical properties and there is no predictability whatsoever from one system to another. Thus in the Norris et al. paper entitled "Toxicological and Environmental Factors Involved in the Selection of Decabromodiphenyl Oxide as a Fire Retardant Chemical", Applied Polymer Symposium No. 22, 195-219 (1973), the authors state: "A growing recognition of the huge annual toll taken by fire is resulting in more stringent flammability requirements for synthetic polymers in a variety of applications. Because of economic constraints and the need to produce flame resistant polymers without total replacement of existing manufacturing processes, increased flame resistance is generally achieved by incorporation of a fire retardant chemical in the finished product. This chemical is usually based on bromine, chlorine, phosphorus, or nitrogen and may either be chemically reacted or physically blended into the product. Since polymer systems differ markedly in both flammability characteristics and physical properties, selection of a suitable flame retardant depends on a variety of factors that severely limits the number of acceptable materials.

"A general class of synthetic polymers that require flame retardancy because of their use in electrical and high temperature applications, but pose severe problems in selecting a suitable flame retardant are the high performance thermoplastic resins such as thermoplastic polyesters, polyphenylene oxides, and acrylonitrile-butadiene-styrene (ABS) terpolymers. Some of the most important criteria for an acceptable flame retardant in these applications are:

"1. It must be as effective as possible to minimize both cost and effect on polymer properties. Use levels may range up to 15% by weight.

"2. It must have sufficient stability to withstand conditions encountered during polymer processing and use. Processing conditions (blending, extrusion, and molding) often involve temperatures exceeding 300° C. The flame retardant must tolerate these conditions without degradation or volatilazation. Also, attention must be given to hydrolytic stability and oxidative degradation, particularly under extended service at high temperatures.

"3. It must be compatible with the base polymer and exert minimal adverse effect on those properties that give the polymer its value. Some of these critical properties are tensile strength, impact strength, heat deflection temperature, shear strength, and flexural modulus.

"4. Finally, the flame retardant must not interfere with attainment of desired product esthetics and form.

"Because of the stringest thermal stability requirements, only a very few compounds have been identified which can meet the necessary performance and economic criteria."

The resultant disadvantages in the utilization of various prior art materials as flame retardants, in general, for plastic compositions include, without limitation, factors such as thermal migration, heat instability, light instability, non-biodegradable, toxicity, discoloration, the large amounts employed in order to be effective, and the unpredictable end results obtained when using the same material in different plastics (note, for example, in Modern Plastics Encyclopedia, ibid, page 650, wherein octabromobiphenyl is suitable for use in polyolefins as a flame retardant therefor, but is not shown for use (or functionally equivalent) as such for the other 27 compositions listed such as ABS; polycarbonates, polystyrene, acrylics and polyurethanes). Thus, it can be seen that the field of flame retardancy is highly sophisticated and consequently requires substantial research effort to achieve a particular desired end result.

In conjunction with the rendition of polyethylene plastics flame retardant the aforegoing discussion is particularly applicable. Furthermore, it is important that, in addition to the retention of good physical characteristics, three characteristics (one of which is critical) of the product (polyethylene) be within certain limitations in order to provide a functional flame retarded product. These three characteristics are (1) light stability (as measured, for example, by Δ E color values, hereinafter defined), (2) flame retardancy (as measured, for example, by UL-94, hereinafter defined, and which is a critical characteristic and limitation), (3) thermal stability (as measured, for example, by certain ASTM tests for decomposition and migration, hereinafter defined). This characteristic of flame retardancy is not an arbitrary item but is a criteria which is strictly adhered to in the polyethylene plastic art and hereinafter explained in more detail, with particular reference to the examples contained herein.

In conjunction with the foregoing discussion, the prior art in general suggests the use of halogen-containing materials as "potential" or "possible" flame retardants for plastic materials. However, the prior art also recognizes that any material must be adjudged on a case by case basis because of the unpredictable results of the end product when any additive is incorporated therein. For example, with reference to the use of a halogenated fire retardant in U.S. Pat. No. 3,658,634, attention is directed to the fact that the patentee specifically points out the disadvantages in the use of a halogen-containing fire retardant. In Column 1, lines 14-17, the patentee states: "Therefore, if it is possible to impart fire-retardancy to the thermoplastic polymers without deteriorating the useful properties of the thermoplastic polymers, they can be widely used in the field of inertia, construction and electric industries." In Column 1, lines 26-32, the patentee states: "--the compounds containing chlorine or bromine atoms to be used as fire retardant agents, are generally sublimated and therefore, the fire retardant agents are sublimated and lost in the process for producing fire-retardant polymers or in after-finishing processes; accordingly, deteriorations of fire-retardancy or difficulties in use tend to occur more often than not."

In Column 1, lines 39-44 the patentee states: "--the compounds containing chlorine or bromine atoms to be used as fire-retardant agents are unstable in most cases when exposed to ultraviolet rays." In Column 1, lines 59-64 the patentee states: "However, as a matter of fact, only very few fire-retardant polymers can be used in actual practice although they are said to have fire-retardant effects, because there are restrictions such as the conditions employed in production attributable to the properties of the fire-retardant agent, or to the properties of the polymers into which they are to be incorporated."

It can be seen, then, from the foregoing discussion and quoted subject matter that the field of flame retardancy is highly sophisticated, unpredictable and requires substantial research to produce an end product (plastic composition) which meets the necessary criteria for utilitarian purposes, particularly under the present day government standards. Thus, there is always a demand for a material which will function as a flame retardant in polyethylene and concurrently will not, by incorporation therein, adversely effect the chemical and/or physical and/or mechanical properties of the resultant polyethylene containing plastic composition (herein also referred to as "polyethylene plastic composition") and also have utility.

The prior art problem of providing a flame retarded polyethylene composition having desired chemical, physical and mechanical properties, in addition to functional utility, has now been substantially solved by the present invention and the above-described disadvantages substantially overcome.

Accordingly, one of the main objects of the present invention is to provide polyethylene plastic compositions which are flame retarded.

Another object of the present invention is to provide a unique three component system for polyethylene plastic compositions which will not substantially adversely effect the chemical and/or physical and/or mechanical properties of said compositions.

A salient object of the present invention is to provide a polyethylene plastic composition which has a certain defined flame retardancy property.

A further object of the present invention is to provide a flame retardant and an enchancing agent which are economical and easy to incorporate into polyethylene plastics without being degraded or decomposed as a result of normal blending or processing operations.

BRIEF DESCRIPTION OF THE INVENTION

It has been found that the foregoing objects can be obtained by the use of a unique three component system, which consists of (a) polyethylene (hereinafter defined), and (b) certain bis-phenoxy compounds (hereinafter defined), and (c) an enhancing agent (hereinafter defined) to subsequently provide flame retarded plastic compositions which exhibit outstanding chemical, physical and mechanical properties.

It is to be understood that the term "flame retarded" as used herein refers and is restricted to a limited definition and that is the reduction in flammability of the plastic composition which contains the three component system. The criticality of this flame retardancy is more specifically set forth herein, with particular reference being made to page 20 herein regarding UL-94 classification (sometimes referred to herein as "values").

DETAILED DESCRIPTION OF THE INVENTION

The particular bis-phenoxy compounds used in the present invention compositions have the formula ##STR2##

In Formula I above, Z is bromine, m and m' are each an integer having a value of 5, and alkylene is -- (CH₂) --, -- (CH₂)₂ -- and -- (CH₂)₃ --.

It is to be understood that only the above compounds fall within Formula I and as heretofore defined are described herein as "bis-phenoxy compounds". A typical bis-phenoxy compound from this group has the following formula: ##STR3##

The compounds of Formula I above, designated as "bis-phenoxy compounds," have been found to be uniquely suitable for polyethylene, particularly "low density polyethylene" (hereinafter defined). However, it was surprising to find that "other bis-phenoxy compounds" were not found suitable in polyethylene as hereinafter disclosed in the examples. These "other bis-phenoxy compounds" include the following: ##STR4##

It is to be specificially understood that those compounds of Formulae III thru IX do not fall within the term "bis-phenoxy compounds" (BPC) used herein, but do fall within the term "other bis-phenoxy compounds" (OBPC).

In general, the compounds BPC (and OBPC) are prepared by reacting a halogenated phenol with a halogenated alkane at elevated temperatures in the presence of a basic material such as alkali metal hydroxides, carbonates, bicarbonates, oxides and hydrides. The preferred alkali metals are potassium and sodium. Where one desires to increase, for example, ease of handling the reaction mass, solvents such as ketones (e.g. acetone, methyl ethyl ketone, and methyl iso-butyl ketone), alcohols (e.g. methanol, ethanol, iso-propyl alcohol, butyl alcohol and glycols), or aqueous solvents (e.g. water, a mixture of water and alcohol and a mixture of water and ketone) can be employed. The desired end product i.e. the BPC and OBPC compounds, can be recovered from the reaction mass via various methods known to those skilled in the art. Where the end product requires recovery via crystallization, various aromatic solvents, such a benzene, toluene, xylene, dichlorobenzene and the like, can be used.

Specifically, the compounds BPC (and OBPC) are prepared according to the following reactions: ##STR5##

In the above reaction, X is halogen, preferably bromine, and alkylene is the same as herein defined.

The above reaction is conducted at temperatures ranging from the freezing point of the initial reaction mass to the boiling point hereof. Preferably the temperatures are from about 40° to about 200° C and more preferably from about 50° to about 175° C. It is to be understood that the reaction can be conducted under sub-atmospheric (e.g. 1/10-8/10 atmospheres) pressure. Preferably, the reaction is carried out at atmospheric pressure.

The above-described processes can be carried out with conventional, readily available chemical processing equipment. For example, a conventional glass-lined vessel provided with heat transfer means, a reflux condenser and a mechanical stirrer can be advantageously utilized in practicing any of the preferred embodiments of the invention described in preparing the BPC/OBPC examples set forth herein.

The amount of bis-phenoxy compound employed in the present invention compositions is any quantity which will effectively render, in conjunction with the enhancing agent, the polyethylene containing composition flame retardant. In general, the amount used is from about 1 to 25% by weight, based on the total weight of the composition. Preferably, the amount employed is from about 5 to about 20% by weight. It is to be understood that any amount can be used as long as it does not substantially adversely effect the chemical and/or physical and/or mechanical properties of the end plastic composition. The amount utilized, however, is such amount which achieves the objectives described herein.

The second component of the three component system, and which is critical therefor, are certain compounds which when used with the bis-phenoxy compounds promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These "enhancing agents" comprise the oxides and halides of groups IVA and VA of the Periodic Table, i.e. oxides and halides of antimony, bismuth, arsenic, tin, lead, germanium, e.g. antimony oxychloride, antimony chloride, antimony oxide, stannic oxide, stannic chloride, arsenous oxide, arsenous chloride, and the like; and organic and inorganic compounds of phosphorus, nitrogen, boron, and sulfur, e.g., triphenyl phosphate, ammonium phosphate, zinc borate, thiourea, urea, stannic sulfide, and the like and oxides and halides of titanium, vanadium, chromium, manganese, iron, niobium, molybdenum copper, zinc, magnesium, e.g. titanium dioxide, titanium chloride, vanadanium pentoxide, chromic bromide, manganous oxide, molybdenum trioxide, ammonium molybdate; and hydrates of the above, e.g., stannic oxide hydrate, lead hydrate; and combinations thereof. The preferred enhancing agents are the oxides of antimony, arsenic and bismuth. However, any compound which on decomposition, as by ignition, yields these oxides would be suitable. Thus some organic antimonates are preferred. The enhancing agents disclosed in U.S. Pat. No. 3,205,196 are also suitable for use.

U.S. Pat. No. 3,205,196, column 2, states that "Antimony oxide is the antimony compound that is presently preferred for use in the present invention. However, many antimony compounds are suitable, inorganic antimony compounds include antimony sulfide sodium antimonite, potassium antimonite, and the like. Many organic antimony compounds are suitable such as the antimony salts of organic acids and their pentavalent derivatives disclosed in copending application Ser. No. 688,143, filed Oct. 4, 1975, now Pat. No. 2,996,528. Compounds of this class include antimony butyrate, antimony valerate, antimony caproate, antimony heptylate, antimony caprylate, antimony pelargonate, antimony caprate, antimony cinnamate, antimony anisate, and their pentavalent dihalide derivatives. Likewise the esters of antimonous acids and their pentavalent derivatives disclosed in copending application Ser. No. 688,108, filed Oct. 4, 1975, now Pat. No. 2,993,924, such as tris(n-octyl) antimonite, tris(2-ethylhexyl) antimonite, tribenzyl antimonite, tris(β-chloroethyl)antimonite, tris(β-chloropropyl) antimonite, tris(β-chlorobutyl) antimonite and their pentavalent compounds are the cyclic antimonites such as trimethylolpropane antimonite, pentaerythritol antimonite, and glycerol antimonite. The corresponding arsenic and bismuth compounds can also be employed."

It is to be understood that such patents as U.S. Pat. Nos. 3,205,196; 2,996,528 and 2,993,924 are to be considered as incorporated herein by reference for all intents and purposes. Without limitation, preferred enhancing agents include Sb₂ O₃, SbCl₃, SbBr₃, SbI₃, SbOCl, As₂ O₃, As₂ O₅, ZnBO₄, BaB₂ O₄.H₂ O, 2.ZnO.3B₂ O₃. 3.5H₂ O and stannic oxide hydrate. The more preferred enhancing agent is antimony trioxide.

The amount of enhancing agent employed in the present invention compositions is any amount which when used with said bisphenoxy compounds will promote a cooperative effect therebetween. In general, the amount employed is from about 0.5 to about 15%, preferably from about 1 to about 10%, by weight, based on the total weight of plastic composition. Higher or lower amounts can be used along as the desire end result is achieved.

The third critical component of the three component system is the polyethylene polymer. It is to be understood that the term polyethylene as used herein means ethylene polymers (such as low and high density polyethylene) including crosslinked, filled and/or reinforced versions of the same. These ethylene polymers include, without limitation, polymers of the formula (CH₂ -- CH₂)_(n) with various degrees of wide branches and including polyethylene (high and low density), crosslinked polyethylene, wax blends, ethylene-vinyl acetate copolymers and blends, ethylene-alkyl acrylate copolymers and blends, carboxyl-containing ethylene copolymers, ionomers, and other derivatives of polyethylene.

The preferred polyethylene polymer is a low density polyethylene (herein referred to as LDPE) which has a density of from about 0.91 to about 0.925 grams per cubic centimeter (g./cm³). These types of LDPE polymers are more specifically described in Encyclopedia of Polymer Science and Technology (Volume 6, Enzymes to Finishing), N. M. Bikales, Editor; 1967--Interscience Publishers (John Wiley & Sons, Inc.) New York; pages 275-329, and which publication is incorporated herein by reference.

Thus the polyethylene used in the present invention compositions is any polyethylene herein defined and which one so desires to flame retard. It is to be understood that the polyethylene used can be a "virgin" material, i.e. substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like, or the polyethylene can have additives (such as those mentioned and described herein) already contained therein or added concurrently with or after the addition of the bis-phenoxy compound(s) and enhancing agent(s).

The bis-phenoxy compounds and enhancing agents can be incorporated into the polyethylene at any processing stage in order to prepare the present invention plastic compositions. In general, this is undertaken prior to fabrication either by physical blending or during the process of forming polyethylene per se. Where one so desires, the bis-phenoxy compounds and/or enhancing agents may be micronized into finely divided particles prior to incorporation into the polyethylene.

It is also within the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promoters; antioxidants; antistatic agents; antimicrobials; colorants; flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid., (in addition to the new class of flame retardants described herein); heat stabilizers; light stabilizers; pigments; plasticizers; preservatives; ultraviolet stabilizers and fillers and additives.

In this latter category, i.e. fillers, there can be mentioned without limitation, materials such as glass; carbon; cellulosic fillers (wood flour, cork and shell flour); calcium carbonate (chalk, limestone, and precipitated calcium carbonate); metal flakes; metallic oxides (aluminum, beryllium oxide and magnesia); metallic powders (aluminum, bronze, lead, stainless steel and zinc); polymers (comminuted polymers and elastomerplastic blends); silica products (diatomaceous earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica); silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including filler, are more fully described in Modern Plastics Encyclopedia, ibid, and which publication is incorporated herein (in toto) by reference.

The amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely effect the desired results derived from the present invention compositions. Thus, the amount used can be zero (0) percent, based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about 0 to about 75% and more specifically from about 1 to about 50%.

With reference to the present invention plastic compositions described herein, one of the critical features thereof is the unusually high flame retardancy thereof. The significance of flame retardancy of plastic compositions is well recognized in the art as heretofor mentioned. However, recent developments in conjunction with the use of flame retardant plastic compositions as judged by the Consumer Product Safety Commission, require a UL-94 value (hereinafter discussed) of V-0 in order to produce a commercially acceptable article of manufacture. The Consumer Product Safety Commission is continuing to set mandatory standards in the field where the plastic compositions are utilized and since about 1970 have increased the criticality of the UL value of plastic compositions. In reaction to the Consumer Product Safety Commission's mandatory standards in this area, the producers of (plastic composition) articles of manufacture are now requiring that said articles have a V-0 value in order to meet new mandatory standards which are anticipated to be activated by federal legislation shortly. Thus, the significance of a plastic composition having a V-0 value is well recognized in the art; note MODERN PLASTICS, September 1974, pages 74-77, December, 1974, page 20, and December, 1975, pages 42-44, 48-50 and 59, and which publications are to be considered as incorporated herein by reference.

In conjunction with the present invention plastic compositions described herein, an important feature thereof is the light stability thereof. The significance of light stability of plastic compositions is recognized in the art, e.g. the publication entitled "The Measurement of Appearance" by Mr. Richard S. Hunter (Hunter Associates Laboratory, Inc., 9529 Lee Highway, Fairfax, Virginia) 1973. Mr. Hunter has been associated with the efforts of defining appearance and color since the 1930's and was for many years an associate of Gardner who is another authority in this field. The following paragraphs from Mr. Hunter's book are set forth in order to demonstrate this light stability significance.

The Judd-Hunter system "of scales for color difference was based on Judd's uniform chromaticity scales triangle. Judd made an instrumental study of a number of woolen swatches rated by dyers for their acceptability as commercial color matches to standard. The NBS unit of color difference was designed by Judd to be the maximum difference commercially acceptable in the textile trade as represented by these dyers at the time when the study was carried out (Judd, 1939). The NBS Unit generally referred to today is not Judd's 1939 unit, but the Hunter 1942 version of the Judd unit with 100 units falling between black and white.

"Since 1942 this unit has been used in terms of a number of the opponent color scales. In a color scale which is already uniform in its visual spacing of lightness and chromaticity, and which has 100 units between black and white as well as rectangular coordinates for chromaticity, color difference in approximate NBS units can be specified in units of that system. The color difference becomes the distance between the two colors in that color space. With rectangular coordinates, the formula is:

    ΔE=√ΔL.sup.2 + Δa.sup.2 + Δb.sup.2

Similarly if only the chromaticity component of difference is desired, the formula is:

    ΔC = √Δa.sup.2 + Δb.sup.2

"Following Judd's proposed unit of color difference, Hunter proposed the measurement of much the same quantity by a photoelectric tristimulus method in 1942. In the next year, Scofield proposed a quantity which was quite a bit easier to compute. Scofield used the reciprocal of the square root of reflectance instead of the reciprocal of the fourth root of reflectance as a multiplier in adjusting reflectance values for uniform lightness scale intervals. This is the only difference between the Scofield and the Judd-Hunter formulas for color difference. (Scofield, 1943).

"In 1948, Hunter started to develop a tristimulus instrument which would read chromaticity dimensions of opponent colors directly. He was seeking to improve the precision and usefulness of results of the tristimulus reflectometers previously used. The R_(d) scales developed in the period 1948 and 1950 did not have a uniform lightness readout but did have direct reading visually uniform a and b scales. The L scales, in which there is approximate perceptual uniformity in all three dimensions, were created in the period 1950-1952 but were not described in a formal publication until 1958. These two sets of Hunter Color Difference Meter scales enjoy wide use because of the fact that they can be read directly from a tristimulus instrument with high precision, and offer instrumental computation of color difference by the ΔE formula given above.

"NBS Unit of Color Difference is defined as: the unit of color difference of the National Bureau of Standards. The unit is about four times as great as the smallest difference observable under ideal conditions. Differences of less than one unit are usually not important in commercial transactions. In Munsell terms, one NBS unit is equivalent to about 0.1 Value step, 0.15 Chroma step, or 2.5 Hue step at Chroma 1.

"Hunter further investigated the use of L', α', β' for color difference measurement. He recognized at this time (which no other color-difference scale before or since has recognized) that perceived color difference will depend on the proximity of the specimens compared and on their glossiness. Accordingly, the 1942 Hunter color difference equation includes factors to account for these variables. It is this equation, with selected constants, that defines the widely used NBS unit of color difference.

"High precision is almost always essential for useful color difference measurements. Only with precise instruments is it possible to measure color differences as small as those the eye can see. Instrument accuracy is also normally a requisite because spectrally inaccurate instruments, even though precise, will give visually inaccurate color difference measurements wherever there are spectral differences between the specimens involved. The ease of obtaining and interpreting values of color difference is another factor which may affect the selection of a procedure.

"Twenty years ago, color difference scales were in demand to serve as a basis for setting one-number tolerances for fading and acceptability of matches. The Index of Fading and NBS unit were used as units.

"Today, the concept of color difference is more refined. One number tolerances are seldom used. Instead, color difference tolerances are designed as boundaries in color space within which acceptable colors must fall. The boundaries do not necessarily correlate with perceptibility of difference but rather with the limits of acceptability. The standard color, furthermore, may not be in the center of the bounded region but may be displaced to one side. For example, where subsequent yellowing may occur, the tolerance for the yellow-blue dimension might be +0.1, -0.8 units.

"Color difference specifications are tighter today and tolerances are smaller. The specification usually treats the color dimensions separately so that a complete specification would contain nine numbers: The three numbers that describe the desired color, and the six numbers that describe the individual plus and minus tolerances. Such tolerances can be reduced to graphs which not only show acceptability but provide a guide to the formulation correction needed to correct an off shade. When the question of acceptability becomes a question of sorting objects according to shade, a graphical chart showing the classification of color values can be quite helpful.

"Although color measurements are frequently used for identification, sorting and recording of color values, the primary uses of tristimulus instruments all involve measurements of fairly small color differences. The most frequent uses of these small color difference measurements are to establish closeness to standard and to give guidance for the adjustment of color mismatches. They are also used in the study of deterioration in a product as a result of exposure and use.

"Spectrophotometers and tristimulus instruments made up the majority of color appearance measuring instruments in use in industry. Spectrophotometers give wavelength-by-wavelength analyses of the reflecting properties of objects, while tristimulus instruments by the use of filters which approximate the Standard Observer functions of the eye, give measurements of color in X, Y, Z terms, or in L, a, b values. Spectrophotometers are essential where color formulation is involved, and metamerism must be comtrolled. However, tristimulus colorimeters and reflectometers provide precise and less expensive means for the routine measurement of color and adjustment of small color differences."

In view of the foregoing quoted subject matter, it can thus be seen that a change in ΔE value of 1 unit constitutes a real change. Note also Japanese patent application (publication 122,456 of 1974) which shows that achieving a color change in ΔE of only 2.3 is significant as it pertains to a polycarbonate polymeric composition; (this value is substantially the same as those ΔE values obtained in polycarbonate tests and which results thereof are shown in Table V herein, i.e. 2.3 versus 2.5 over the control). Both of these publications (i.e. the Japanese Pat. No. 122,456 and the Hunter book) are to be considered as incorporated herein by reference. It is to be noted also that a lower ΔE value is more desired and the higher ΔE value is least desired. This ΔE value is not an abstract value, however, since one must compare it with the ΔE values of the "control" plastic composition. One of the desired ΔE values would be where both the ΔE values of the "control" plastic composition "without additives"--(i.e. without flame retardant and enhancing agent) and the plastic composition with said additives are substantially the same or the latter has a lower value.

EXAMPLES (Including Comparative Data)

The following examples are presented to demonstrate the uniqueness of the present invention compositions as contrasted to other plastic compositions containing the same (present invention) bis-phenoxy compounds (BPC), "other bis-phenoxy compounds" (OBPC) and prior art compounds with or without an enhancing agent. These examples also show unpredictability, via the end results, in using any halogenated material, much less the same material, in several different plastics.

Referring to Example I, this example sets forth the comparison of a low density polyethylene plastic (LDPE) with seven other polymer systems and includes substantial detail with particular reference to physical properties including flammability.

Referring to Example II, this compares a related polymer system (polypropylene), having incorporated therein the "other bis-phenoxy compounds" (Formulae III and IV, page 11), and an enhancing agent with four other polymers containing the same "other bis-phenoxy compounds" and enhancing agent. The four comparative polymers are polyacrylonitrile, acrylonitrile-butadiene-styrene (ABS), nylon and polymethylmethacrylate. As will be seen from the results hereinafter set forth, the four other polymers had no flame retardant efficacy when incorporating the "other bis-phenoxy compounds" (OBPC) and enhancing agents, whereas the ABS system did, utilizing certain OBPC compounds, and so demonstrates the unpredictability of any material in any polymer system, particularly a related material in a related polymer system, i.e. OBPC compounds (Formulae III and IV) in polypropylene.

Specifically and in conjunction with the results set forth in Table II, it can be seen that while certain "other bis-phenoxy compounds" (Formulae III and IV, page 11) were effective in an ABS system, these same compounds were not effective in a polypropylene polymer.

The results, thus, are another indication of the unpredictability of additives in polymer systems and correspond to the subject matter set forth in "Modern Plastic Encyclopedia", ibid., regarding the use of octabromobiphenyl in one polymer but not shown for use (or functionally equivalent) in numerous other materials.

EXAMPLE I

Solid samples of eight different plastic compositions separately containing certain prior art compounds, a present invention bis-phenoxy compound and "other bis-phenoxy compounds", all with or without the herein described enhancing agents, are prepared according to the procedure set forth hereinafter, and are subjected to the following tests in order to ascertain comparative properties of the resultant plastic compositions:

    ______________________________________                                         (1) Flammability                                                                   (a) Oxygen Index, O.I.                                                                           ASTM Test No. D-2863-70                                      (b) UL-94         UL-94 Procedure described                                                      herein and dated February 1,                                                   1974.                                                    (2) Light Stability                                                                (Weather Ometer)  Procedure described herein-                                  (a) Visual rank   after                                                        (1 is the highest)                                                             (b) Gardner Colorimeter                                                        ("ΔE" Values)                                                        (3) Initial Color     Visual color observation                                                       immediately after injection                                                    molding.                                                 (4) Visual Migration  Visual observation of sur-                                                     face haze presence.                                      (5) TGA and Isotherm  Procedure described here-                                                      inafter.                                                 (6) Melt Flow         ASTM Test No. 1238-70.                                   (7) Notched Izod Impact                                                                              ASTM Test D256-72a; and                                  (8) Heat Distortion                                                                Temperature (HDT) ASTM Test No. D648-72.                                   ______________________________________                                    

Regarding item (a) above, i.e. light stability, the results obtained via the "Visual" rank include any color changes which occurred in the molded materials tested from a combination of processing and exposure to the xenon arc.

Each of the aforementioned Tests is a standard test in the art and are utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retardant composition for commercial application. All of these Tests are to be considered as incorporated herein by reference.

The different polymers utilized along with trade names and corresponding suppliers are listed below.

    ______________________________________                                         Polymer        Trademark    Supplier                                           ______________________________________                                         Polyethylene,  Bakelite     Union Carbide                                       Low Density (LDPE)                                                                            DPD-3900*                                                      ABS            Cycolac T-2098                                                                              Borg-Warner                                        Polycarbonate  Lexan 141    General Electric                                   Nylon 6        Zytel 211    DuPont                                             Polypropylene  Profax 6523  Hercules                                           Terephthalate polyester                                                                       Valox 310    General Electric                                   Polyphenylene oxide,                                                                          Noryl 731    General Electric                                    modified (PPO)                                                                Polystyrene    Bakelite     Union Carbide                                       (high impact) HIPS                                                                            TMDE-6500                                                      ______________________________________                                          *Note Page 329, Encyclopedia of Polymer Science and Technology, ibid,          regarding this polymer as a LDPE.                                        

The concentration of the additives (i.e. prior art compounds) (designated PAC), present invention bis-phenoxy compounds (designated BPC) or "other bis-phenoxy compounds" (designated OBPC), with or without an enhancing agent (designated EA) and the respective Table Nos. listing the pertinent data are shown below. The Table numbers are shown in parenthesis.

    ______________________________________                                                   PAC, BPC or        ONLY                                              Polymer   OBPC/EA--Sb.sub.2 O.sub.3 %                                                                     PAC, BPC or OBPC                                    ______________________________________                                         LDPE      20/5 (I)                                                             ABS       15/5 (II)        20/0 (III)                                          Polycarbonate                                                                            3/1 (V)          + 30/0 (IV)                                         Nylon     12/4 (VI)                                                            Polypropylene                                                                            12/4 (VII)                                                           Polyester 12/4 (VIII)      16/0 (IX)                                           PPO       9/3 (X)                                                              PPO       9/3 Pigmented TiO.sub.2 (XI)                                         HIPS      12/4 (XII)       16/0 (XIII)                                                                    + 30/0 (XIV)                                        ______________________________________                                    

All percentages (%) shown are on a weight basis, based on the total weight of the plastic composition.

The identification of the prior art compounds (PAC) listed as A, B, C, D, E and F in the Tables are shown below:

    ______________________________________                                         PAC (Letter)                                                                             FORMULA                                                              ______________________________________                                         A         C.sub.6 Cl.sub.5 C.sub.6 Cl.sub.5                                              decachlorobiphenyl                                                   B         C.sub.6 Br.sub.5 OC.sub.6 Br.sub.5                                             Bis-(pentabromophenyl)ether                                          C         C.sub.6 Br.sub.6                                                               Hexabromobenzene                                                     D         C.sub.6 Br.sub.5 CH.sub.2 Br                                                   Pentabromobenzyl bromide                                             E         C.sub.6 H.sub.2 Br.sub.2 (OCH.sub.3)C(CH.sub.3).sub.2 C.sub.6                  H.sub.2 Br.sub.2 (OCH.sub.3)                                                   Bis-2,2-(3,5-dibromo-4-methoxyphenyl)propane                         F         C.sub.6 H.sub.2 Br.sub.3 OCH.sub.2 CBr=CBrCH.sub.2 OC.sub.6                    H.sub.2 Br.sub.3                                                               Trans 1,4-Bis(2,4,6-tribromophenoxy)-2,3-                                      dibromo-2-butene                                                     ______________________________________                                    

The present invention bis-phenoxy compound (BPC) listed in the Tables under Present Invention as II corresponds to that compound listed on page 10 of this specification.

The "other bis-phenoxy compounds" (OBPC) listed in the Tables under such title, as III through IX, correspond to those compounds listed on pages 11, 12 and 13 of this specification.

The control (base resin) is the particular designated polymer without the PAC, BPC, OBPC, or EA.

The plastic materials which are subject to the above described tests, are prepared in the following manner. With the exception of "base resin", the particular additive (PAC, OBPC or BPC, and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic by adding both to a Brabender mixer ("Plastic-Corder", Torque Rheometer, Model PLV-150, C. W. Brabender Instruments Inc., South Hackensack, N.J.). The mixer is equipped with a pair of roller type blades positioned within a head provided with heat transfer means.

The resultant mixture is heated to about 245° C.; at this temperature, it is in a molten state. The percentages by weight of each component utilized in the respective formulations are listed in the Tables. Each formulation is discharged from the mixer and upon cooling solidifies and is ground into chips. The chips are subjected to injection molding in a one (1) ounce Newbury Injection Molder, Model HI 30 RS, manufactured by Newbury Industries, Inc.; Newbury, Ohio by placing said chips therein and utilizing a 60 second molding cycle with a ram pressure of 2000 psi. The chips contained in said molder are subjected to heat transfer means supplied thereto in order to melt said chips, and the melted chips are then rammed into a mold in order to provide solid samples (after cooling) for testing.

Portions of the solid samples of each respective formulation prepared according to the above described procedure are subjected to two different flammability tests, i.e. UL 94 and ASTM D-2863-70. The UL 94 is, in general, the application of a burner to a test specimen (strip) for a certain period of time and observation of combustion, burning, and extinguishment. This procedure is fully set forth in Underwriters' Laboratories bulletin entitled UL 94, Standard for Safety, First Edition, September 1972 and which is incorporated herein by reference. ASTM No. D-2863-70 is a flammability test which correlates the flammability of a plastic specimen to the available oxygen in its immediate environment; this correlation is stated as an Oxygen Index, O.I., level predicated upon the percent oxygen in the gaseous medium which is required to just provide a steady state of continuous burning of the plastic specimen. This ASTM method is fully described in 1971 Annual Book of ASTM Standards--Part 27, published by the American Society for Testing and Materials, 1916 Race Street, Philadelphia, Pa.; this publication is to be considered as incorporated (in toto) herein by reference. The UL 94 test is the more critical test as it is the test generally used to determine the suitability of thermoplastics for commercial applications.

Samples of each formulation are subjected to temperature (thermal) stability tests via the use of thermal gravimetric analysis (TGA). This test employs the use of a "Thermal Balance", model TGS-1, Perkin-Elmer Corporation, Norwalk, Connecticut and an electrical balance, Cahn 2580 model, Cahn Instrument Company, Paramount, California. The conditions of this TGA test are listed in the following Tables.

Samples of each formulation are also subjected to light stability tests via the use of a "Weather-Ometer", model 25/18 W. R., Atlas Electrical Devices Company, Chicago, Illinois. Utilizing an operating temperature of 145° F and a 50% relative humidity, each sample is subjected to the indicated number of hours of "simulated daylight" via the use of a Xenon arc. This Test shows whether there is any significant discoloration in any sample tested and the end results are set forth in ΔE values.

The results of all of this comparative testing are shown in Tables I through XIV.

                                      Table I                                      __________________________________________________________________________                                                               Present                             Control                                                                             Prior Art             Other Bis-phenoxy                                                                              Invention            Resin                                                                               LDPE      (Base                                                                               Compounds             Compounds       BPC                  Additive                                                                            20/5      Resin)                                                                              A B   C   D   E   F   III IV  IX  VII II                   __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                               18.0   28.0                                                                               29.0                                                                               27.0                                                                               26.5                                                                               26.5                                                                               26.0                                                                               28.0                                                                               25.5                                                                               27.5                                                                               26.5                 UL-94 1/8" thickness                                                                          HB     V-0 V-2 V-2 V-2 V-2 V-2 V-0 V-2 V-2 V-0                  Xenon Arc                                                                      Weather-Ometer (Ranked)                                                        Injection Molded                                                                              Natural                                                                               Off-                                                                               Light                                                                              Off-                                                                               White                                                                              Cream                                                                              White                                                                              White   Off-                                                                               White                Initial Color         White                                                                              Grey                                                                               White                   White                    Visual Migration XInitial                                                                            None                                                                               Yes Yes None                                                                               None                                                                               None                                                                               Yes     None                                                                               None                 X7 days               None                                                                               Yes Yes None                                                                               Yes None                                                                               Yes     None                                                                               None                 TGA 5% wt. loss ° C                                                                    302    330 248 248 265 267 305 308     339 332                  Isotherm 48 hr. 150° C                                                                 0      0   1.84                                                                               2.42                                                                               0.78                                                                               0.66                                                                               0.26                                                                               0.41    0.34                                                                               0.16                 Melt Flow g/10 min.                                                            Conditions "G" 200 C 5000g                                                     Notched Izod Impact                                                                           NB     NB  NB      NB  NB      NB  NB      NB                   ft. - lbs/in. 1/2 × 1/8                                                                 >6.6   >7.1                                                                               >7.9                                                                               3.31                                                                               >7.3                                                                               >8.3                                                                               2.12                                                                               >8.8    3.00                                                                               8.1                  Heat Deflection Temp.                                                          ° F at 264 psi                                                          Annealed at 180° F                                                      Concentrate Compounding                                                        Temperature, ° F                                                                       400    400 400 400 400 400 450 400 400 400 400                  Injection Molding     450-                                                     Temperature, ° F                                                                       430    410 410 410 410 410 410 410 410 410 430                  Gardner Color Value, ΔE                                                  After 100 hours, Xenon Arc                                                                    0.4    9.8 8.5 4.4 2.1 7.5 3.9 1.3 2.4 6.2 3.0                  __________________________________________________________________________

                                      Table II                                     __________________________________________________________________________                                                                 Pre-                                                                           sent                                                                           Inven-                             Control                                                                             Prior Art                              tion               Resin ABS       (Base                                                                               Compounds            Other Bis-phenoxy                                                                                BPCpounds          Additive 15/5   Resin)                                                                              A    B  C   D  E  F  III                                                                               IV IX V  VIII                                                                              VII                                                                               III                __________________________________________________________________________     Oxygen Index, %                                                                at 73° F 18.5 21.5 28.0                                                                              27.5                                                                               35.0                                                                              26.0                                                                              34.5                                                                              30.5                                                                              28.0                                                                              30.0                                                                              31.0                                                                              36.0                                                                              33.5                                                                              30.5               UL-94 1/8"                                                                     thickness       HB   HB   V-0                                                                               V-0 V-O                                                                               HB V-0                                                                               V-0                                                                               V-0                                                                               V-0                                                                               V-0                                                                               V-0                                                                               V-0                                                                               V-0                Xenon Arc                                                                      Weather-Ometer (Ranked)                                                                        5    6    12 10  13 3  11 7  8  4  2  1     9                  Injection Molded     Off- Off-                                                                              Off-   Off-                                                                              Light                                   Initial Color   White                                                                               White                                                                               White                                                                             White                                                                              Tan                                                                               White                                                                             Cream                                                                             White                                                                             White                                                                             White                                                                             White                                                                             White                                                                             White                                                                             White              Visual Migration                                                                  Initial           None None                                                                              None                                                                               None                                                                              None                                                                              None                                                                              None                                                                              None        None                                                                              None                 7 days             None None                                                                              None                                                                               None                                                                              None                                                                              None                                                                              None                                                                              None        None                                                                              None               TGA 5% wt. loss ° C                                                                     329  266  307                                                                               249 261                                                                               271                                                                               274                                                                               285                                                                               290         307                                                                               310                Isotherm 72 hr., 150° C                                                                 1.83 48 hr.  48 hr.    1.27                                                                              1.11                                                      0.415   0.727                                             Melt Flow g/10 min.                                                            Conditions "G" 200 ° C, 5,000g                                                          3.2  3.6  4.0                                                                               4.5 8.3                                                                               9.9                                                                               4.9                                                                               8.2                                                                               6.7         4.6                                                                               3.4                Notched Izod Impact                                                            ft. lbs/in. 1/2 × 1/8                                                                    3.27 1.62 1.40                                                                              1.19                                                                               1.56                                                                              1.62                                                                              1.23                                                                              1.93                                                                              2.12                                                                              1.32                                                                              2.08                                                                              1.92                                                                              2.20                                                                              1.19               Heat Deflection Temp.                                                          ° F at 264 psi                                                                          192  189  187                                                                               190 184                                                                               171                                                                               185                                                                               180                                                                               176         186                                                                               190                Annealed at 180° F                                                      Concentrate Compounding                                                        Temperature, ° F                                                                             400  400                                                                               400 400                                                                               400                                                                               400                                                                               450                                                                               350                                                                               400                                                                               400                                                                               400                                                                               400                                                                               400                Injection Molding                                                              Temperature, ° F                                                                        450  450  450                                                                               450 450                                                                               450                                                                               430                                                                               450                                                                               450                                                                               450                                                                               450                                                                               450                                                                               450                                                                               450                Gardner Color Value, ΔE                                                  After 100 hours, Xenon Arc                                                                     6.5  3.9  20.1                                                                              11.9                                                                               12.7                                                                              4.6                                                                               8.6                                                                               6.7                                                                               7.9                                                                               1.1                                                                               0.9                                                                               4.1                                                                               11.6                                                                              7.3                __________________________________________________________________________

                                      Table III                                    __________________________________________________________________________                     Con-                                     Present                               trol Prior Art               Other Bis-phenoxy                                                                          Invention             Resin ABS       (Base                                                                               Compounds               Compounds   Compound              Additive 20/0   Resin)                                                                             A     B  C   D   E   F   III IV  VII II                    __________________________________________________________________________     Oxygen Index, %                                                                at 73° F 18.5 20.5                                                                               24.5                                                                               24.0                                                                               27.0                                                                               22.5    24.0                                                                               22.5                                                                               25.0                                                                               27.0                  UL-94 1/8" thickness                                                                           HB   HB  HB  V-0 V-0 HB      HB  HB  HB  V-0                   Xenon Arc                                                                      Weather-Ometer (Ranked)                                                                        1    5   7   6   8   1       2   3       4                     Injection Molded                                                                               White                                                                               Off-                                                                               Off-                                                                               Off-                                                                               Tan White                                                                              De- White                                                                              White                         Initial Color        White                                                                              White                                                                              White       com-        White                                                                              Off-White             Visual Migration Initial                                                                            None                                                                               None                                                                               None                                                                               None                                                                               None                                                                               posed                                                                              None                                                                               None                                                                               None                                                                               None                  7 days                                                                         TGA 5% wt. loss ° C                                                     Isotherm 72 hr., 150° C                                                 Melt Flow g/10 min.                                                            Conditions "G" 200° C,                                                  5,000g                                                                         Notched Izod Impact                                                            ft.lbs/in. 1/2 ×  1/8                                                                    3.27 1.40                                                                               1.43                                                                               1.17                                                                               1.15                                                                               1.97    3.27                                                                               4.18                                                                               3.52                                                                               1.45                  Heat Deflection Temp.                                                          ° F at 264 psi,                                                         Annealed at 180° F                                                      Concentrate Compounding                                                        Temperature, ° F                                                                             400 400 400 400 400 400 400 400 400 400                   Injection Molding                                                              Temperature, ° F                                                                        450  450 450 450 420 450     450 450 450 450                   Gardner Color Value, Δ E                                                 After 100 hours, Xenon Arc                                                                     6.5  8.0 19.8                                                                               11.1                                                                               8.5 4.6     4.4 5.2 11.4                                                                               5.6                   __________________________________________________________________________

                                      Table IV                                     __________________________________________________________________________                                                              Present                               Control                                                                             Prior Art               Other Bis-phenoxy                                                                          Invention             Resin ABS       (Base                                                                               Compounds               Compounds   Compound              Additive 30/0   Resin)                                                                              A   B   C   D   E   F   III IV  VII II                    __________________________________________________________________________     Oxygen Index, %                                                                at 73° F 18.5 21.5                                                                               30.0                                                                               30.0                                                                               32.0                                                                               27.0                                                                               30.0                                                                               33.5                                                                               34.0                                                                               38.5                                                                               35.5                  UL-94 1/8" thickness                                                                           HB   HB  V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0                   Xenon Arc                                                                      Weather-Ometer (Ranked)                                                                        3    5   10  8   11  1   7   4   2   9   6                                          Egg Egg Egg                         Egg                   Injection Molded                                                                               White                                                                               Shell                                                                              Shell                                                                              Shell                                                                              Light                                                                              White                                                                              Light                                                                              White                                                                              White   Shell                                      White                                                                              White                                                                              White                                                                              Brown   Tan             White                 Visual Migration Initial                                                       7 days                                                                         TGA 5% wt. loss ° C                                                     Isotherm 72 hr., 150° C                                                 Melt Flow g/10 min.                                                            Conditions "G" 200° C,                                                  5,000g                                                                         Notched Izod Impact                                                            ft. lbs/in. 1/2 ×  1/8                                                                   3.27 1.06                                                                               1.08                                                                               1.09                                                                               1.50                                                                               1.42                                                                               1.19                                                                               2.49                                                                               3.65                                                                               2.46                                                                               1.13                  Heat Deflection Temp.                                                          ° F at 264 psi,                                                         Annealed at 180° F                                                      Concentrate Compounding                                                                        --   440 440 440 392 392 356 440 400 410 440                   Temperature, ° F                                                        Injection Molding                                                              Temperature, ° F                                                                        450  450 450 450 400 430 400 450 450 430 450                   Gardner Color Value, Δ E                                                 After 100 hours, Xenon Arc                                                                     6.5  1.4 9.0 2.6 6.5 1.6 2.5 2.6 1.2 3.4 0.8                   __________________________________________________________________________

                                      Table V                                      __________________________________________________________________________                    Con-                                      Present                              trol                                                                               Prior Art               Other Bis-phenoxy                                                                            Invention             Resin Polycarbonate                                                                           (Base                                                                              Compounds               Compounds     Compound              Additive 3/1   Resin)                                                                             A    B   C   D   E   F  III  IV  VII  II                    __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                               25.0                                                                               36.5 41.5                                                                               39.5                                                                               39.5                                                                               37.0   36.5 37.5                                                                               40.0 40.0                  UL-94 1/8 " thickness                                                                         HB  V-2  V-0 V-2 V-2 V-0    V-0  V-0 V-0  V-0                   Xenon Arc                                                                      Weather-Ometer (Ranked)                                                                       1   5    10  8   9   3      2    4   6    7                     Injection Molded                                                                              Clear                                                                              Light                                                                               Light                                                                              Light                                                                              Cream                                                                              Light                                                                              De-                                                                               Off- Cream                                                                              Off-                       Initial Color      Cream                                                                               Cream                                                                              Cream   Cream                                                                              com-                                                                              White    White                                                                               Off-White                                Perhaps              po-                                                                               Perhaps  Perhaps                    Visual Migration Initial                                                                          Slight                                                                              None                                                                               None                                                                               None                                                                               None                                                                               si-                                                                               Slight                                                                              None                                                                               Slight                                                                              None                  7 days             None None                                                                               None                                                                               None                                                                               None                                                                               tion                                                                              None None                                                                               None None                  TGA 5% wt. loss ° C                                                                    427 381  379 375 366 378    398  374 381  388                   Isotherm 24 hr. 200° C                                                                 0.394                                                                              1.20 0.5529                                                                             1.78                                                                               1.18                                                                               1.12   0.664                                                                               0.655                                                                              0.388                                                                               0.326                 Melt Flow g/10 min.                                                            Conditions 275° C,                                                                     9.8 11.8 12.7                                                                               18.8                                                                               17.2                                                                               16.8   8.8  17.4                                                                               12.2 11.4                  1,200g                                                                         Notched Izod Impact                                                            ft. lbs/in. 1/2 × 1/8                                                                   16.50                                                                              6.64 8.54                                                                               2.73                                                                               1.02                                                                               3.16   16.98                                                                               7.25                                                                               11.45                                                                               9.41                  Heat Deflection Temp.                                                          ° F at 264 psi,                                                                        279 265  267 260 259 262    265  259 265  268                   Annealed at 200° F                                                                                              De-                                    Concentrate Compounding                 grad-                                  Temperature, ° F                                                                           500  480 480 500 500 ed at                                                                             500  500 500  500                                                           500                                    Injection Molding                                                              Temperature, ° F                                                                       520 520  520 520 520 520    520  520 520  520                   Gardner Color Value, ΔE                                                  After 48 hours, Xenon Arc                                                                     1.1 4.7  22.2                                                                               10.1                                                                               6.7 3.8    3.6  3.6 12.4 9.6                   __________________________________________________________________________

                                      Table VI                                     __________________________________________________________________________                                                              Present                              Control                                                                             Prior Art                Other Bis-phenoxy                                                                          Invention             Resin Nylon 6  (Base                                                                               Compounds                Compounds   Compound              Additive 12/4  Resin)                                                                              A   B   C    D   E   F   III IV  VII II                    __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                               21.5 26.0                                                                               28.5                                                                               29.0             24.5                                                                               Mold-                                                                              De- 27.5                  UL-94 1/8" thickness                                                                          HB   V-2 V-0 V-2              V-2 ing com-                                                                               V-0                   Xenon Arc                        Did De- Did     Prob-                                                                              posed                     Weather-Ometer (Ranked)          Not com-                                                                               Not     lems                                                                               Dur-                      Injection Molded                                                                              Natural           Mold                                                                               posed                                                                              Mold                                                                               Off-                                                                               De- ing                       Initial Color  (white)                                                                             Cream                                                                              Cream                                                                              Cream            White                                                                              com-                                                                               Mold-                                                                              Cream                 Visual Migration Initial                                                                           None                                                                               None                                                                               None             None                                                                               posed                                                                              ing None                  7 days              None                                                                               None                                                                               None             None        None                  TGA 5% wt. loss ° C                                                                    237  219 219 204              214         220                   Isotherm 48 hr. 150° C                                                                 5.67 4.70                                                                               4.60                                                                               4.76             4.49        4.97                  Melt Flow g/10 min.                                                            Conditions "G" 200° C                                                   5000g                                                De-                       Notched Izod Impact                                  com-                      ft.lbs/in. 1/2 × 1/8                                                                    3.09 1.85                                                                               1.66                                                                               1.60             2.54    posed                                                                              2.20                  Heat Deflection Temp.                                Dur-                      ° F at 264 psi,                                                                        125  137 133 135              132     ing 136                   Annealed at 100° F                            Mold-                     Concentrate Compounding                              ing                       Temperature, ° F                                                                            440 440 440      440     440         440                   Injection Molding                                                              Temperature, ° F                                                                       480  480 480 480      450     480         480                   Gardner Color Value, Δ E                                                 After 100 hours, Xenon Arc                                                                    0.9  2.0 3.7 2.5              2.4         7.9                   __________________________________________________________________________

                                      Table VII                                    __________________________________________________________________________                 Con-                                         Present                           trol                                                                               Prior Art                  Other Bis-phenoxy                                                                            Invention             Resin Polypropylene                                                                        (Base                                                                              Compounds                  Compounds     Compound              Additive 12/4                                                                              Resin)                                                                             A    B    C   D   E    F   III  IV   VII II                    __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                            17.5                                                                               21.0 24.0 25.0                                                                               24.0                                                                               20.5 31.5                                                                               21.5 23.5 23.5                                                                               23.0                  UL-94 1/8" thickness                                                                       HB  HB   V-2  HB  V-2 HB   V-0 HB   V-2  HB  HB                    Xenon Arc                                                                      Weather-Ometer                                                                             1   4    11   9   10  5    8   3    2    7   6                     (Ranked)                                                                       Injection Molded                                                                           Clear                                                                              Off- Off- Cream                                                                              Cream                                                                              Off- Cream                                                                              Off- Off- Cream                                                                              Off-White             Initial Color   White                                                                               White        White    White                                                                               White                                          Perhaps           Perhaps  Perhaps                                                                             Perhaps                        Visual Migration Initial                                                                       Slight                                                                              Perhaps                                                                             None                                                                               None                                                                               Slight   Slght                                                                               Slight                                                                              None                                                                               None                  7 days          Perhaps                                                                             Slight                                                                              None                                                                               None                                                                               None     Perhaps                                                                             Perhaps                                                                             None                                                                               None                                  Slight                                                                              None                  Slight                                                                              Slight                         TGA 5% wt. loss ° C                                                                 272 264  274  256 252 260  269 275  273  281 276                   Isotherm 48 hr. 150° C                                                              0.00                                                                           0.20                                                                               0.937                                                                               0.493                                                                               3.7 13.6                                                                               2.14 0.756                                                                              0.607                                                                               0.873                                                                               0.768                                                                              0.33                  Melt Flow g/10 min.                                                            Conditions "L", 230° C,                                                             5.2 9.3  6.8  9.8 9.3 9.9  17.7                                                                               10.4 8.9  9.7 6.4                   2,160g                                                                         Notched Izod Impact                                                            ft.lbs/in. 1/2 × 1/8                                                                 1.22                                                                               1.19 1.21 1.12                                                                               1.16                                                                               1.13 1.10                                                                               0.96 1.07 1.07                                                                               1.20                  Heat Deflection Temp.                                                          ° F at 66 psi,                                                                      246 253  240  276 240 235  267 267  257  262 277                   Annealed at 194° F                                                      Concentrate                                                                    Compounding     400  420  400 360 450  420 400  400  450 400                   Temperature, ° F                                                        Injection Holding                                                                          440 440  440  440 440 440  400 440  440  440 440                   Temperature, ° F                                                        Gardner                                                                        Color Value, Δ E                                                                     0.5 5.3  12.8 10.0                                                                               8.8 5.6  7.3 2.7  2.7  8.0 4.8                   After 48 hours,                                                                Xenon Arc                                                                      __________________________________________________________________________

                                      Table VIII                                   __________________________________________________________________________                    Con-                                      Present                              trol                                                                               Prior Art                Other Bis-phenoxy                                                                           Invention             Resin Polyester                                                                               (Base                                                                              Compounds                Compounds    Compound              Additive 12/4  Resin)                                                                             A   B    C   D   E   F   III IV   VII II                    __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                               22.0                                                                               28.0                                                                               32.0 32.0                                                                               32.0                                                                               26.0    30.0                                                                               29.0 30.0                                                                               32.0                  UL-94 1/8" thickness                                                                          HB  V-2 V-0  V-0 V-0 V-2 De- V-2 V-2  V-0 V-0                   Xenon Arc                               com-                                   Weather-Ometer (Ranked)                                                                       1   5   9    7   8       po- 3   2    6   4                     Injection Molded                                                                              White                                                                              Off-                                                                               Off- Off-                                                                               Cream                                                                              Cream                                                                              si- White                                                                              White                                                                               Off-                      Initial Color      White                                                                              White                                                                               White       tion         White                                                                              Cream                 Visual Migration Initial                                                                          None                                                                               None None                                                                               None                                                                               None    None                                                                               None None                                                                               None                  7 days             None                                                                               None None                                                                               None                                                                               None    None                                                                               None None                                                                               None                  TGA 5% wt. loss ° C                                                                    369 281 346  266 292 305     311 330  353 351                   Isotherm 24 hr. 200° C                                                                 0.576                                                                              1.97                                                                               0.115                                                                               3.66                                                                               4.67                                                                               2.89    1.99                                                                               0.606                                                                               0   0.446                                0.489                                                           Melt Flow g/10 min.                                                                           15.0                                                                               11.5                                                                               12.8 10.8                                                                               22.0                                                                               16.5    6.5 25.8 36.7                                                                               11.3                  Conditions "H", 230° C,                                                 1,200 g                                                                        Notched Izod Impact                                                                           1.51                                                                               1.04                                                                               1.00 1.07                                                                               0.96                                                                               1.12    1.19                                                                               1.33 1.26                                                                               0.90                  ft.lbs/in. 1/2 × 1/8                                                     Heat Deflection Temp.                                                          ° F at 264 psi                                                                         123 122 127  127 121 123     117 122  125 139                   Annealed at 100° F                                                      Concentrate Compounding                                                                           450 450  450 450 450     450 450  450 450                   Temperature, ° F                                                        Injection Molding                                                              Temperature, ° F                                                                       470 460 460  460 470 470     460 470  470 460                   Gardner Color Value, Δ E                                                 After 24 hours, Xenon Arc                                                                     1.9 7.8 22.6 7.3 8.5 1.9     3.4 3.1  8.0 4.2                   __________________________________________________________________________

                                      Table IX                                     __________________________________________________________________________                                                       Present                                     Control                                                                             Prior Art         Other Bis-phenoxy                                                                          Invention                    Resin Polyester                                                                               (Base                                                                               Compounds         Compounds   Compound                     Additive 16/0  Resin)                                                                              A   B   C   D E F III   IV    II                           __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                               22.0 28.0                                                                               23.0                                                                               28.5      27.5  27.5  27.5                         UL-94 1/8" thickness                                                                          HB   V-2 V-2 V-2       V-2   V-2   V-2                          Xenon Arc                                                                      Weather-Ometer (Ranked)                                                        Injection Molded                                                               Initial Color  White                                                                               Off-                                                                               Light                                                                              Light     Off-  White White                                            White                                                                              Tan Grey      White                                    Visual Migration Initial                                                       7 days                                                                         TGA 5% wt. loss ° C                                                     Isotherm 24 hr., 200° C                                                 Melt Flow g/10 min.                                                            Conditions "H", 230° C,                                                 1,200g                                                                         Notched Izod Impact                                                                           1.51 0.93                                                                               1.32                                                                               1.13      1.19  1.33  1.13                         ft. lbs/in. 1/2 × 1/8                                                    Heat Deflection Temp.                                                          ° F at 264 psi,                                                         Annealed at 100° F                                                      Concentrate Compounding                                                                            450 450 450       470   470   450                          Temperature, ° F                                                        Injection Molding                                                                             470  460 460 460       460   460   460                          Gardner Color Value, Δ E                                                 After 24 hours, Xenon Arc                                                      __________________________________________________________________________

                                      Table X                                      __________________________________________________________________________                                                      Other   Present                                  Control                                                                             Prior Art                Bis-phenoxy                                                                            Invention             Resin PPO          (Base                                                                               Compounds                Compounds                                                                              Compound              Additive 9/3       Resin)                                                                              A   B   C   D   E     F  III IV  II                    __________________________________________________________________________     Oxygen Index, %    26.5 25.0                                                                               30.0                                                                               28.0                                                                               31.0                                                                               27.0 30.0                                                                               27.5                                                                               29.0                                                                               27.0                  at 73° F                                                                UL-94 1/8" thickness                                                                              V-1  V-1 V-0 V-0 V-0 V-0  V-0 V-0 V-0 V-0                   Xenon Arc                                                                      Weather-Ometer (Ranked)                                                        Injection Molded   Brown                                                                               Brown                                                                              Brown                                                                              Brown                                                                              Brown                                                                              Brown                                                                               Brown                                                                              Brown                                                                              Brown                                                                              Brown                 Initial Color                                                                                                          Perhaps                                Visual Migration X Initial                                                                             None                                                                               None                                                                               None                                                                               None                                                                               Slight                                                                              None                                                                               None                                                                               None                                                                               None                  X 7 days                None                                                                               None                                                                               None                                                                               None                                                                               None None                                                                               None                                                                               None                                                                               None                  TGA 5% wt. loss ° C                                                                        281  249 294 244 243 262  261 277 276 279                   Isotherm 24 hr. 200° C                                                                     1.87 4.07                                                                               2.21                                                                               5.00                                                                               3.88                                                                               3.19 5.40                                                                               3.08                                                                               3.19                                                                               2.35                  Melt Flow g/10 min.                                                                               1.4  3.3 2.1 2.6     3.7      3.8 3.0 1.9                   Conditions (not recorded)                                                      Notched Izod Impact                                                                               4.02 2.39                                                                               2.44                                                                               2.44                                                                               1.94                                                                               2.97 1.77                                                                               2.50                                                                               2.60                                                                               1.89                  ft.lbs/in. 1/2 × 1/8                                                     Heat Deflection Temp.                                                                             209  196 205 200 200 177  194 193 190 203                   ° F at 264 psi,                                                         Annealed at 235° F                                                      Concentrate Compounding 450 450 450 450 450  450 450 450 450                   Temperature, ° F                                                        Injection Molding  450  450 450 450 450 450  450 450 450 450                   Temperature, ° F                                                        Gardner Color Value, ΔE                                                  After   hours, Xenon Arc                                                       __________________________________________________________________________

                                      Table XI                                     __________________________________________________________________________                   Control                                                                             Prior Art             Other Bis-phenoxy                                                                          Present Invention         Resin PPO     (Base                                                                               Compounds             Compounds   Compound                  Additive 9/3 (Pigmented)                                                                     Resin)                                                                              A B   C   D   E   F   III IV  VII II                        __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                              25.0   32.0                                                                               31.0                                                                               33.5                                                                               26.5                                                                               32.5                                                                               28.0                                                                               28.5                                                                               27.5                                                                               30.0                      UL-94 1/8" thickness                                                                         HB   V-0                                                                              V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0                           Xenon Arc     1      9   6   8   1   7   3   2   5   4                         Injection Molded                                                                             Light  Light                                                                              Light   Light                                                                              Dark                                                                               Light                                                                              Light                                                                              Light                         Initial Color Tan    Tan Tan Tan Tan Tan Tan Tan Tan Light Tan                 Visual Migration X Initial                                                                   None   None                                                                               None                                                                               None                                                                               None                                                                               None                                                                               None                                                                               None                                                                               None                                                                               None                      X 7 days      None   None                                                                               None                                                                               None                                                                               None                                                                               None                                                                               None                                                                               None                                                                               None                                                                               None                      TGA 5% wt. loss ° C                                                                   389    335 284 291 311 275 338 324 330 337                       Isotherm 24 hr. 200°  C                                                               0.299  0.420                                                                              0.893                                                                              0.865                                                                              0.587                                                                              1.02                                                                               0.556                                                                              0.272                                                                              0.363                                                                              0.476                     Melt Flow g/10 min.                                                            Notched Izod Impact                                                            ft. lbs/in. 1/2 × 1/8                                                                  3.24   2.14                                                                               2.00                                                                               1.19                                                                               2.02                                                                               1.40                                                                               2.16                                                                               2.18                                                                               1.83                                                                               1.82                      Heat Deflectio Temp.                                                           ° F at 264 psi,                                                                       246    233 226 227/ 210                                                                           221 210 207 2.28                                                                               237                           Annealed at 200° F                                                      Concentrate Compounding                                                                      450    450 450 450 450 450 450 450 450 450                       Temperature, ° F                                                        Injection Molding                                                              Temperature, ° F                                                                      460    460 460 460 460 460 460 460 460 460                       Gardner Color Value, ΔE                                                  After 48 hours, Xenon Arc                                                                    3.6    13.3                                                                               9.2 9.0 5.9 14.8                                                                               5.3 4.9 9.3 6.9                       __________________________________________________________________________

                                      Table XII                                    __________________________________________________________________________                                                                Pre-                                                                           sent                                                                           Inven-                         Control                                                                             Prior Art                  Other Bis-phenoxy                                                                              tion                Resin HIPS (Base                                                                               Compounds                  Compounds       BPC                 Additive 12/4                                                                             Resin)                                                                              A   B    C    D   E     F  III IV  IX  VII II                  __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                           18.5 20.0                                                                               26.0 23.5 27.0                                                                               23.0 25.0                                                                               21.0                                                                               23.0                                                                               26.0                                                                               24.0                                                                               25.5                UL-94 1/8" thickness                                                                      HB   HB  V-0  V-0  V-0 HB   V-2 HB  HB  HB  V-0 V-0                 Xenon Arc                                                                      Weather-Ometer                                                                            1    5   11   10   12  3    9   4   6   7       8                   (Ranked)                                                                       Injection Molded                                                                          White                                                                               Light                                                                              Cream                                                                               Grey Light                                                                              White                                                                               Tan Off-                                                                               Off-                                                                               Off-    Off-                Initial Color   Cream    Cream                                                                               Cream        White                                                                              White                                                                              White                                                                              White                                                                              White               Visual Migration    Perhaps                                                                             Perhaps  Perhaps                                       X Initial None None                                                                               Slight                                                                              Slight                                                                              None                                                                               Slight                                                                              None                                                                               None                                                                               None    None                                                                               None                 X 7 days  None None                                                                               None None None                                                                               None None                                                                               None                                                                               None    None                                                                               None                TGA 5% wt. loss ° C                                                                322  270 325  263  254 279  277 304 305     328 325                 Isotherm 48 hr.,                                                                          0.582                                           0.22                150° C                                                                             0.410                                                                               1.44                                                                               0.301                                                                               1.04 3.12                                                                               1.17 0.885                                                                              0.940                                                                              0.758   0.223                   Melt Flow g/10 min.                                                            Conditions "G" 200°                                                                6.2  11.0                                                                               8.8  10.4 13.3                                                                               11.1 15.8                                                                               10.7                                                                               13.8    12.2                                                                               7.1                 C, 5,000g                                                                      Notched Izod Impact                                                            ft.lbs/in. 1/2 × 1/8                                                                2.12 1.61                                                                               1.71 1.66 1.65                                                                               1.64 1.25                                                                               1.76                                                                               1.63                                                                               1.72                                                                               1.66                                                                               1.69                Heat Deflection                                                                Temp. ° F at 264 psi,                                                              182  171 180  171  165 157  172 172 157         177                 Annealed at 160° F                                                      Concentrate                                                                    Compounding                                                                               --   400 400  400  400 400  400 450 400 400 400 450                 Temperature, ° F                                                        Injection Molding                                                                         450  450 450  450  450 430  430 450 430 450 450 450                 Temperature, ° F                                                        Gardner Color Value,                                                           ΔE After 24 hours,                                                                  0.7  17.6                                                                               33.6 23.9 34.3                                                                               7.0  11.0                                                                               11.0                                                                               20.9                                                                               16.3                                                                               12.7                                                                               14.4                Xenon Arc                                                                      __________________________________________________________________________

                                      Table XIII                                   __________________________________________________________________________                  Control                                                                             Prior Art               Other Bis-phenoxy                                                                          Present Invention        Resin HIPS   (Base                                                                               Compounds               Compounds   Compound                 Additive 16/0                                                                               Resin)                                                                              A   B   C   D   E   F   III IV  VIII                                                                               II                       __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                             18.5 18.5                                                                               22.0                                                                               22.0    21.5    21.0                                                                               21.5                                                                               22.0                                                                               22.0                     UL-94 1/8" thickness                                                                        HB   HB  V-2 HB      HB      HB  HB  HB  HB                       Xenon Arc                                                                      Weather-Ometer (Ranked)                                                                     1    2   9   7       5       3   6   8   4                        Injection Molded                                                                            White                                                                               Off-                                                                               Cream                                                                              Cream                                                                              De- White                                                                              De- Off-                                                                               White                                                                              White                                                                              Cream                    Initial Color     White       compo-  compo-                                                                             White                                Visual Migration X Initial                                                                       None                                                                               None                                                                               None                                                                               sition                                                                             None                                                                               sition                                                                             None                                                                               None                                                                               None                                                                               None                     X 7 days          None                                                                               None                                                                               None    None    None                                                                               None                                                                               None                                                                               None                     TGA 5% wt. loss ° C                                                     Isotherm 72 hr. 150° C                                                  Melt Flow g/10 min.                                                            Conditions "G" 200 C                                                           5000g                                                                          Notched Izod Impact                                                            ft.lbs/in. 12 × 1/8                                                                   2.12 1.64                                                                               1.69                                                                               1.58    1.59    1.62                                                                               1.60                                                                               1.71                                                                               1.66                     Heat Deflection Temp.                                                          ° F at 264 psi,                                                         Annealed at 160° F                                                      Concentrate Compounding                                                        Temperature, ° F                                                                          400 400 400     400     400 400 400 400                      Injection Molding                                                                           450  450 450 450     450     450 450 450 450                      Temperature, ° F                                                        Gardner Color Value, ΔE                                                  After 24 hours, Xenon Arc                                                                   0.7  19.4                                                                               25.9                                                                               23.2    21.7    34.0                                                                               30.5                                                                               40.0                                                                               17.8                     __________________________________________________________________________

                                      Table XIV                                    __________________________________________________________________________                    Control                                                                             Prior Art              Other Bis-phenoxy                                                                         Present Invention        Resin HIPS     (Base                                                                               Compounds              Compounds  Compound                 Additive 30/0  Resin)                                                                              A   B   C   D   E   F  III IV  VII                                                                               II                       __________________________________________________________________________     Oxygen Index, %                                                                at 73° F                                                                               18.5 21.0                                                                               25.5                                                                               25.5                                                                               30.0                                                                               25.0                                                                               27.0                                                                              27.0                                                                               25.0                                                                               27.0                                                                              32.0                     UL-94 1/8" thickness                                                                          HB   HB  V-0 V-0 V-0 V-0 V-0                                                                               V-0 V-0 V-0                                                                               V-0                      Xenon Arc                                                                      Weather-Ometer (Ranked)                                                                       1    5   10  7   9   2   8  4   6   11 3                        Injection Molded                                                                              Trans-                                                                              Biege                                                                              Light                                                                              Grey                                                                               Brown                                                                              Light                                                                              Tan                                                                               Off-                                                                               Off-   Light Beige              Initial Color  luscent  Grey        Tan    White                                                                              White                           Visual Migration X Initial                                                     X 7 days                                                                       TGA 5% wt. loss ° C                                                     Isotherm 72 hr., 150° C                                                 Melt Flow g/10 min.                                                            Conditions "G" 200° C, 5,000g                                           Notched Izod Impact                                                            ft.lbs/in. 1/2 × 1/8                                                                    2.12 1.10                                                                               1.21                                                                               1.43                                                                               1.45                                                                               1.27                                                                               1.11                                                                              1.39                                                                               1.35                                                                               1.46                                                                              R 1.08                                                                         1.10                     Heat Deflection Temp.                                                          ° F at 264 psi,                                                         Annealed at 160° F                                                      Concentrate Compounding                                                        Temperature, ° F                                                                            450 450 430 356 392 356                                                                               450 400 392                                                                               450                      Injection Molding                                                              Temperature, ° F                                                                       450  430 430 410 380 400 380                                                                               430 410 420                                                                               430                      Gardner Color Value, ΔE                                                  After 24 hours, Xenon Arc                                                                     0.7  22.4                                                                               29.7                                                                               15.8                                                                               10.4                                                                               5.1 12.1                                                                              17.2                                                                               24.9                                                                               36.3                                                                              6.8                      __________________________________________________________________________

Referring to Tables I through XIV in general, it is readily apparent that the incorporation of additives in polymer systems is highly unpredictable. Even in the same polymer, "structurally related" prior art compounds, "other bis-phenoxy compounds" and the present invention bis-phenoxy compounds produced completely different results. However, out of all the data shown therein it is clear that the combination of the present invention bis-phenoxy compound and enhancing agent result in an unexpected, superior, flame retarded polyethylene plastic composition which has commercial application.

Specifically, Table I shows the results of testing a polyethylene polymer containing 20% PAC, OBPC, or BPC and 5% EA. The polyethylene/BPC/EA combination is the only one of the OBPC or BPC which produced V-0 (UL-94) with good thermal stability (e.g. no visual migration) and, in general color values ΔE, on an overall average basis, substantially closer to the control (without additives). Thus these particular BPC compounds are unique; note the V-2 (poor values of the OBPC. While the OBPC (Formula IV) yielded a V-0 (UL-94) rating, the thermal stability was quite poor as noted by the visual migration test. While B yielded a V-0 (UL-94) composition, the ΔE Value was excessively high and thus nonapplicable for most commercial uses. C, D, E, and F show nonefficacy (close to the HB ratings like the control) thereof as flame retardants and again point out the non-predictability of additives incorporated in either the same or various polymers.

EXAMPLE II

Regarding Formulation Nos. 1-10 in Table XV, a virgin polyacrylonitrile plastic material, (T-61 polymer crumb, a product of American Cyanamid and characterized as a copolymer of 93% by weight acrylonitrile and about 7% by weight methyl methacrylate) is utilized as the base resin in order to prepare 10 formulations (plastic compositions). With the exception of formulation No. 1, the particular "other bis-phenoxy compound" (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic (which is dried to remove moisture therefrom) by adding both to a Waring blender which contains acetone as a dispersing liguid. The resultant mixture, after blending for 3 minutes, is poured into evaporation dishes and the acetone evaporated, first at room temperature (20°-25° C) for 60 minutes and followed by oven drying at 60° C for 1 hour.

The percentages by weight of each component utilized in the respective formulations are listed in Table XV. Each formulation is discharged from the evaporation dish and is ground into powder. The powder is subjected to compression molding in a Wabash press by placing said powder between two platens, the bottom of which contains four equal size depressions 3 inches by 5 inches by 1/8 inch deep. The top platen is then placed over the bottom platen and heat transfer means supplied thereto in order to melt said powder and thus provide solid samples (after cooling) for testing. The temperature and ram pressure utilized are respectively 100° C and 30 tons.

A polypropylene plastic material, (Hercules Pro-fax®6523grade of polypropylene) is utilized as the base resin in order to prepare 13 formulations (plastic compositions)--Nos. 11-23 shown in Table XV. With the exception of formulation No. 11, the particular "other bis-phenoxy compound" (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic and solid samples prepared according to the procedure set forth in Example I.

A virgin nylon 6 plastic material, (Zytel®211, a product of E. I. du Pont de Nemours and Co., Wilmington, Deleware) is utilized as the base resin in order to prepare 7 formulations (plastic compositions--Nos. 24-30 shown in Table XV. With the exception of formulation No. 24, the particular "other bis-phenoxy compound" (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic and solid samples prepared according to the procedure set forth in Example I.

Regarding Formulation Nos. 31-33 in Table XV, a virgin polymethylmethacrylate plastic material, Plexiglass®V (811) a commercially available product of Rohm and Haas Company, Philadelphia, Pennsylvania and being substantially free of additives, is utilized as the base resin in order to prepare 3 formulations (plastic compositions). With the exception of formulation No. 31, the particular "other bis-phenoxy compound" (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic and solid samples prepared according to the procedure set forth in Example I.

Referring to Formulation Nos. 34-37 in Table XV, an acrylonitrile-butadiene-styrene (ABS) polymer plastic material, Marbon TP-2098, a product of Marbon Division, Borg-Warner Corporation, Washington, West Virginia, and which is a slight process variation of their commercially available "T" grade ABS polymer, is utilized as the base resin in order to prepare four (4) formulations (plastic compositions). These formulations, Nos. 34-37, are prepared in accordance with the procedure described in ASTM D-1897-68.

Portions of the samples of each respective formulation (Nos. 1-37, Table XV) prepared respectively according to the above described procedures are then subjected to two different standard flammability tests, i.e. UL 94 and ASTM D-2863-70, i.e. Oxygen Index, O.I.

The results of these flammability tests are shown in Table XV.

                  TABLE XV                                                         ______________________________________                                         FLAMMABILITY DATA FOR DIFFERENT PLASTIC                                        COMPOSITIONS CONTAINING                                                        "OTHER BIS-PHENOXY COMPOUNDS" WITH AND                                         WITHOUT ENHANCING AGENTS                                                       ______________________________________                                         FORM-  "OTHER       EN-       OXY-                                             ULA-   BIS-PHENOXY  HANCING   GEN                                              TION   COMPOUNDS"   AGENT     INDEX  UL 94                                     NO.    FORMULA %    Sb.sub.2 O.sub.3, %                                                                      %      VALUE                                     ______________________________________                                         Polyacrylonitrile Polymer  --                                                  1.     --      0        0       22.5   SB                                      2.     IV      2        0       23.5   SB                                      3.     IV      5        0       23.8   SB                                      4.     IV      10       0       24.0   SB                                      5.     IV      5        5       25.3   SB                                      6.     IV      5        10      25.3   SB                                      7.     III     2        0       23.0   SB                                      8.     III     5        0       23.0   SB                                      9.     III     10       0       24.0   SB                                      10.    III     5        5       25.0   SB                                      Polypropylene Polymer                                                          11.    --      0        0       18.0   Burns                                   12.    IV      15       0       20.0   SB                                      13.    IV      15       5       22.8   SB                                      14.    IV      20       5       26.0   SB                                      15.    IV      25       0       24.0   SB                                      16.    IV      25       5       26.0   SB                                      17.    III     15       0       19.0   SB                                      18.    III     15       5       22.0   SB                                      19.    III     20       5       25.0   SB                                      20.    III     25       0       23.0   SB                                      21.    III     25       5       25.0   SB                                      22.    IV      20       10      25.0   SB                                      23.    III     20       10      24.0   SB                                      Nylon                                                                          24.    --      0        0       23.0   SB                                      25.    IV      10       0       23.5   SB                                      26.    IV      10       3       24.5   SB                                      27.    IV      13       3       27.5   SE-2                                    28.    III     10       0       23.5   SB                                      29.    III     10       3       24.0   SB                                      30.    III     13       3       27.0   SE-2                                    Polymethylmethacrylate Polymer                                                 31.    --      0        0       18.0   SB                                      32.    III     15       0       20.5   SB                                      33.    III     15       5       20.5   SB                                      Acrylonitrile-Butadiene-Styrene (ABS) Polymer                                  34.    --      0        0       19.0   HB(SB)                                  35.    III     15       0       27.0   HB(SB)                                  36.    III     15       5       32.5   V-O(SE-O)                               37.    IV      15       5       35.0   V-O(SE-O)                               ______________________________________                                    

Referring to Table XV, the "other bis-phenoxy compound" formula III or IV relates to the structural formulae heretofor set forth; and the UL-94 values are on a graduated scale wherein the highest degree to lowest degree of flame retardancy is respectively SE-0 (V-0), SE-1 (V-1), SE-2 (V-2), SB (HB) and Burns.

The results shown in Table XV demonstrate the unexpected and completely unpredictable results of the plastic composition (Formulations Nos. 36 and 37) containing a three component system which consists of the "other bis-phenoxy compounds," an enhancing agent and acrylonitrile-butadiene-styrene (ABS) polymer as compared to the use of such "other bis-phenoxy compound" with or without an enhancing agent in a polyacrylonitrile polymer, a polymethlmethacrylate polymer, a nylon polymer, and a polypropylene polymer, the latter four of which polymers show substantially no increase in flame retardancy via the use of said "other bis-phenoxy compounds," with or without an enhancing agent.

Specifically referring to the polyacrylonitrile polymer compositions Nos. 1-10, formulation No. 1 (the control) has an UL value of SB. In Nos. 2-10, the use of the particular "other bis-phenoxy compound" (with or without the enhancing agent) results, within experimental accuracy, in no increase in flame retardancy via incorporation of 2, 5, or 10% of the "other bis-phenoxy compound" per se.

Regarding the use of an enhancing agent in formulation Nos. 5 and 6, the results obtained therefrom show that there is no increase in flame retardancy. Thus, for example, No. 1 (control) has an UL value of SB and Nos. 5 and 6 (which have different enhancing agent levels, 5% versus 10%) have also an UL value of SB. In viewing the results of No. 3 (5%-0%) and No. 5 (5%-5%), it can be seen that even the use of the enhancing agent does not increase flame retardancy in a polyacrylonitrile polymer.

With reference to the polypropylene polymer compositions Nos. 11 thru 23, it can readily be seen from the UL 94 values that the incorporation of the particular "other bis-phenoxy compound" therein resulted in substantially little, if any, increase in flame retardancy as compared to the control, considering the experimental accuracy. Even the use of an enhancing agent did not result in an increase in flame retardancy, note No. 12-SB and No. 13-SB. Predicated upon this data, it is thus seen that the incorporation of the "other bis-phenoxy compounds" (with or without an enhancing agent) in a polypropylene results in no flame retardant efficacy.

Specifically referring to the nylon polymer compositions--Nos. 24-30, formulation No. 24 (the control) had an UL value of SB. In Nos. 25-28, the use of the particular "other bis-phenoxy compound" results in no increase in flame retardancy via incorporation of 10% (SB versus SB) of the "other bis-phenoxy compound" per se.

Regarding the use of an enhancing agent in formulation Nos. 26, 27, 29, and 30, the results obtained therefrom show there is substantially little, if any, increase in flame retardancy. Thus, for example, No. 1 (control) has an UL value of SB and Nos. 26 and 29 also have an UL value of SB. While Nos. 27 and 30 each have an UL value of SE-2, this is not considered a significant increase and thus even the use of the enhancing agent does not result in flame retardancy efficacy.

With reference to the polymethylmethacrylate polymer compositions Nos. 31, 32 and 33, it can readily be seen from the UL values, i.e. all SB, that the incorporation of the particular "other bis-phenoxy compound" therein results in no increase in flame retardancy as compared to the control. Even the use of an enhancing agent did not result in an increase in flame retardancy. Consequently, it can readily be seen that the incorporation of the "other bis-phenoxy compounds" in a polymethylmethacrylate results in no flame retardant efficacy.

The most unexpected results in flame retardancy were obtained via the incorporation of the particular "other bis-phenoxy compounds" and enhancing agents in an acrylonitrile-butadiene-styrene (ABS) polymer. Referring specifically to formulation Nos. 34 through 37, the control (formulation No. 34) had an UL value of HB(SB). Notwithstanding the incorporation of 15% (No. 35) of the particular "other bis-phenoxy compound" per se in the ABS polymer, there still results an UL value of SB. Use of the enhancing agent with both "other bis-phenoxy compounds" formulae III and IV, in formulation Nos. 36 and 37 results in an unexpected UL value change from SB (No. 35) to SE-0/V-0 (No. 36) and SE-0/V-0 (No. 37). In view of these results, it was quite unexpected that the ABS polymer system, having incorporated therein the particular "other bis-phenoxy compounds" and enhancing agent would show such superior flame retardant efficacy based on the results obtained from the performance of the other four (4) polymers, i.e. polyacrylonitrile, polypropylene, nylon and polymethylmethacrylate polymer systems having the same "other bis-phenoxy compounds" and enhancing agents incorporated therein. By the same token and with particular reference to the results disclosed in Example I, the "other bis-phenoxy compound" -OBPC (formulae III) did not exhibit any substantial flame retardancy efficacy (V-2) in polyethylene (LDPE) at the "20/5" level (Table I) whereas a present invention bis-phenoxy compound exhibited superior and unexpected efficacy (V-0) and good thermal stability at the same level of usage.

Furthermove, if the OBPC did not have any efficacy in polypropylene, it would certainly be unpredictable that the OBPC, much less a related material, would have any efficacy in polyethylene.

Consequently, it can readily be seen that it is not possible to predict the efficacy and/or functionality of any halogen-containing material (which may be suggested as a flame retardant) in any polymeric system until one actually conducts a substantial research program thereon and ascertains certain properties of the "flame retarded" system and its utility.

EXAMPLE III

The procedure of Example I is repeated except that the BPC used is 1,1-bis(2,3,4,5,6-pentabromophenoxy)methane instead of 1,2-bis(2,3,4,5,6-pentabromophenoxy)ethane (Formula II). Substantially the same results are obtained using the "methane" BPC as those using the "ethane" BPC.

EXAMPLE IV

The procedure of Example I is again repeated except that the BPC used is 1,3-bis(2,3,4,5,6-pentabromophenoxy)propane instead of 1,2-bis(2,3,4,5,6-pentabromophenoxy)ethane (Formula II). Substantially the same results are obtained using the "propane" BPC as those using the "ethane" BPC.

EXAMPLE V

The procedure of Examples I through IV are repeated except that the enhancing agent used is zinc borate instead of antimony oxide. Substantially the same results are obtained using zinc borate as those using atimony oxide.

EXAMPLE VI

The (present invention) bis-phenoxy compounds described herein are subjected to toxicity tests and it is found that these compound are not toxic orally, not irritating to the eye and not irritating to the skin, all as measured by the guidelines of the Federal Hazardous Substances Act. Furthermore, rat feeding studies indicate these materials are not biologically persistent, an important property to minimize ecological imbalance.

In summary, the results shown on Tables I through XV are reviewed with aforementioned criteria, i.e. UL-94 rating V-0 and physical properties (such as thermal stability), and are presented in Table XVI in terms of whether there is commercial utility, (taking into consideration most importantly V-0 rating and then physical/mechanical properties) i.e. similar to those results shown for octabromobiphenyl in Modern Plastics Encyclopedia, ibid. Table XVI sets forth more vividly the difference between the present bis-phenoxy compounds, other bis-phenoxy compounds and the prior art and also the different results obtained when different polymers have the same additives incorporated therein; and also confirming those specific observations regarding the difference in polymer systems as noted by the Norris et al. paper, ibid.

                                      TABLE XVI                                    __________________________________________________________________________     FLAME RETARDANT EFFICACY OF DIFFERENT ADDITIVES IN DIFFERENT POLYMER           SYSTEMS                                                                        (IS THERE COMMERCIAL UTILITY BASED ON A POLYETHYLENE SYSTEM                    __________________________________________________________________________     CRITERIA?)                                                                                                                     Present                                       Prior Art                        Invention                      Polymers       Compounds + Enhancing Agents                                                                     OBPC + EA      BPC + EA                       I. Present Invention                                                                          A  B  C  D  E  F  III                                                                               IV IX VIII                                                                              VII                                                                               II                             __________________________________________________________________________     Polyethylene (LDPE)                                                                              ?* No No No No No Yes                                                                               No    No Yes                            II. Comparative Polymers                                                       ABS            No ?* ?* ?* No Yes                                                                               Yes                                                                               Yes                                                                               Yes                                                                               Yes                                                                               Yes                                                                               Yes                            Polycarbonate  No No No No Yes                                                                               No Yes                                                                               Yes      Yes                                                                               Yes                            Nylon          No Yes                                                                               No    No    No No       No Yes                            Polypropylene  No No No No No Yes                                                                               No No       No No                             Polyester      No ?* ?* ?* No No No No       Yes                                                                               Yes                            Polyphenylene oxide (PPO)                                                                        ?* ?* ?* Yes                                                                               ?* Yes                                                                               Yes      Yes                                                                               Yes                            Polystyrene (HIPS)                                                                            No No No No No No No No No    No Yes                            Polyacrylonitrile                No No                                         Polymethylmethacrylate           No No                                         __________________________________________________________________________      *Perhaps; very high ΔE values                                      

In view of the foregoing Examples and remarks, it is seen that the plastic compositions, which incorporate a three component system (including the bis-phenoxy compounds), possess characteristics which have been unobtainable in the prior art. Thus, the use of these particular bis-phenoxy compounds and an enhancing agent in polyethylene as flame retardants therefor is quite unique since it is not possible to predict the effectiveness and functionality of any particular material in any polymer system until it has actively undergone incorporation therein and the resultant plastic composition evaluated according to certain criteria such as UL-94 and various ASTM Standards. Furthermore, it is necessary, in order to have commercial utility, that the resultant flame retarded plastic composition possess characteristics such as being non-toxic and not biologically persistent. Use of the bis-phenoxy compounds and an enhancing agent in polyethylene has accomplished all of these objectives.

Thus, in order to meet the needs and standards of commerce, it is necessary that a successful candidate fulfill all of the requirements outlined above, not just a selected group. It was totally unexpected that these specific bis-phenoxy compounds meet these requirements in all aspects contrary to the expectations of the suggested teachings of the prior art.

The above examples have been described in the foregoing specification for the purpose of illustration and not limitation. Many other modifications and ramifications will naturally suggest themselves to those skilled in the art based on this disclosure. These are intended to be comprehended as within the scope of this invention. 

What is claimed is:
 1. A plastic composition comprising a three component system consisting of (1) polyethylene polymer, (2) a bis-phenoxy compound, which functions as a flame retardant for said composition, having the formula ##STR6## wherein (a) Z is bromine; (b) m and m' are independent and are integers having a value of 5 and (c) alkylene is selected from the group consisting of --(CH₂)--, --(CH₂)₂ --, and --(CH₂)₃ --, and (3) a flame retardant enhancing agent.
 2. The composition as set forth in claim 1 wherein the amount of said bis-phenoxy compound employed is from about 1 to about 25% by weight, based on the total weight of said composition.
 3. The composition as set forth in claim 2 wherein the enhancing agent is selected from the group consisting of oxides and halides of Groups IV A and V A of the Periodic Table of Elements.
 4. The composition as set forth in claim 3 wherein the enhancing agent is antimony oxide.
 5. A plastic composition comprising a three component system consisting of (1) low density polyethylene polymer, (2) a bis-phenoxy compound, which functions as a flame retardant for said composition, having the formula ##STR7## wherein (a) Z is bromine; (b) m and m' are independent and are integers having a value of 5 and (c) alkylene is --(CH₂)-- and (3) a flame retardant enhancing agent.
 6. The composition as set forth in claim 5 wherein the amount of said bis-phenoxy compound employed is from about 1% to about 25% by weight, based on the total weight of said composition.
 7. The composition as set forth in claim 6 wherein the enhancing agent is selected from the group consisting of oxides and halides of Groups IV A and V A of the Periodic Table of Elements.
 8. The composition as set forth in claim 7 wherein the enhancing agent is antimony oxide.
 9. A plastic composition comprising a three component system consisting of (1) low density polyethylene polymer, (2) a bis-phenoxy compound, which functions as a flame retardant for said composition, having the formula ##STR8## wherein (a) Z is bromine; (b) m and m' are independent and are integers having a value of 5 and (c) alkylene is --(CH₂)₃ -- and (3) a flame retardant enhancing agent.
 10. The composition as set forth in claim 9 wherein the amount of said bis-phenoxy compound employed is from about 1 to about 25% by weight, based on the total weight of said composition.
 11. The composition as set forth in claim 10 wherein the enhancing agent is selected from the group consisting of oxides and halides of Groups IV A and V A of the Periodic Table of Elements.
 12. The composition as set forth in claim 11 wherein the enhancing agent is antimony oxide.
 13. A plastic composition comprising a three component system consisting of (1) low density polyethylene polymer, (2) a bis-phenoxy compound, which functions as a flame retardant for said composition, having the formula ##STR9## wherein (a) Z is bromine; (b) m and m' are independent and are integers having a value of 5 and (c) alkylene is --(CH₂)₂ -- and (3) a flame retardant enhancing agent.
 14. The composition as set forth in claim 13 wherein the amount of said bis-phenoxy compound employed is from about 1% to about 25% by weight, based on the total weight of said composition.
 15. The composition as set forth in claim 14 wherein the enhancing agent is selected from the group consisting of oxides and halides of Groups IV A and V A of the Periodic Table of Elements.
 16. The composition as set forth in claim 15 wherein the enhancing agent is antimony oxide.
 17. A flame retarded, shaped plastic composition comprising a three component system which consists of (a) a low density polyethylene polymer, (b) a bis-phenoxy compound which is 1,2-bis (2,3,4,5,6-pentabromophenoxy)ethane and (c) an enhancing agent selected from the group consisting of oxides of antimony, arsenic and bismuth; with the proviso that said plastic composition is further characterized by having a flammability rating of SE-0 (V-0) as determined by the UL-94 procedure described in this specification.
 18. A substantially white, flame retarded, injection molded plastic composition comprising a three component system which consists of (a) low density polyethylene polymer, (b) a bis-phenoxy compound which is 1,2-bis(2,3,4,5,6-pentabromophenoxy) ethane and (c) an enhancing agent selected from the group consisting of oxides of antimony, arsenic and bismuth; with the proviso that said plastic composition is further characterized by having a flammability rate of SE-0 (V-0) as determined by the UL-94 procedure described in the specification.
 19. The composition as set forth in claim 18 wherein (a) the bis-phenoxy compound is present in an amount of from about 1% by weight to about 25% by weight, based on the total weight of said composition and (b) the enhancing agent is antimony trioxide and is present in an amount of from about 1% by weight to about 10% by weight, based on the total weight of said composition.
 20. The composition as set forth in claim 19 wherein the amount of said bis-phenoxy compound is about 20% by weight, based on the total weight of said composition, and said enhancing agent is present in an amount of about 5% by weight, based on the total weight of said composition.
 21. The composition as set forth in claim 19 wherein said composition is characterized by having no migration over a period of approximately seven days and a ΔE Color Value of about 3.0 as determined by test procedure set forth in the specification. 